Antialgal activity of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes against the marine alga Ulva.

Marine biofouling has detrimental effects on the environment and economy, and current antifouling coatings research is aimed at environmentally benign, non-toxic materials. The possibility of using contact-active coatings is explored, by considering the antialgal activity of cationic poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes. The antialgal activity was investigated via zoospore settlement and sporeling growth assays of the marine algae Ulva linza and U. lactuca. The assay results for PDMAEMA brushes were compared to those for anionic and neutral surfaces. It was found that only PDMAEMA could disrupt zoospores that come into contact with it, and that it also inhibits the subsequent growth of normally settled spores. Based on the spore membrane properties, and characterization of the PDMAEMA brushes over a wide pH range, it is hypothesized that the algicidal mechanisms are similar to the bactericidal mechanisms of cationic polymers, and that further development could lead to successful contact-active antialgal coatings.

Charged hydrophilic polymer brushes and their relevance for understanding marine biofouling.

The resistance of charged polymers to biofouling was investigated by subjecting cationic (PDMAEMA), anionic (PSPMA), neutral (PHEMA-co-PEG10MA), and zwitterionic (PSBMA) brushes to assays testing protein adsorption; attachment of the marine bacterium Cobetia marina; settlement and adhesion strength of zoospores of the green alga Ulva linza; settlement of barnacle (Balanus amphitrite and B. improvisus) cypris larvae; and field immersion tests. Several results go beyond the expected dependence on direct electrostatic attraction; PSPMA showed good resistance towards attachment of C. marina, low settlement and adhesion of U. linza zoospores, and significantly lower biofouling than on PHEMA-co-PEG10MA or PSBMA after a field test for one week. PDMAEMA showed potential as a contact-active anti-algal coating due to its capacity to damage attached spores. However, after field testing for eight weeks, there were no significant differences in biofouling coverage among the surfaces. While charged polymers are unsuitable as antifouling coatings in the natural environment, they provide valuable insights into fouling processes, and are relevant for studies due to charging of nominally neutral surfaces.

Hydrogel-coated feed spacers in two-phase flow cleaning in spiral wound membrane elements: a novel platform for eco-friendly biofouling mitigation.

Biofouling is still a major challenge in the application of nanofiltration and reverse osmosis membranes. Here we present a platform approach for environmentally friendly biofouling control using a combination of a hydrogel-coated feed spacer and two-phase flow cleaning. Neutral (polyHEMA-co-PEG10MA), cationic (polyDMAEMA) and anionic (polySPMA) hydrogels have been successfully grafted onto polypropylene (PP) feed spacers via plasma-mediated UV-polymerization. These coatings maintained their chemical stability after 7 days incubation in neutral (pH 7), acidic (pH 5) and basic (pH 9) environments. Anti-biofouling properties of these coatings were evaluated by Escherichia coli attachment assay and nanofiltration experiments at a TMP of 600 kPag using tap water with additional nutrients as feed and by using optical coherence tomography. Especially the anionic polySPMA-coated PP feed spacer shows reduced attachment of E. coli and biofouling in the spacer-filled narrow channels resulting in delayed biofilm growth. Employing this highly hydrophilic coating during removal of biofouling by two-phase flow cleaning also showed enhanced cleaning efficiency, feed channel pressure drop and flux recoveries. The strong hydrophilic nature and the presence of negative charge on polySPMA are most probably responsible for the improved antifouling behavior. A combination of polySPMA-coated PP feed spacers and two-phase flow cleaning therefore is promising and an environmentally friendly approach to control biofouling in NF/RO systems employing spiral-wound membrane modules.

Antifouling properties of oligo(lactose)-based self-assembled monolayers.

The antifouling (AF) properties of oligo(lactose)-based self-assembled monolayers (SAMs), using four different proteins, zoospores of the green alga Ulva linza and cells of the diatom Navicula incerta, were investigated. The SAM-forming alkylthiols, which contained 1, 2 or 3 lactose units, showed significant variation in AF properties, with no differences in wettability. Non-specific adsorption of albumin and pepsin was low on all surfaces. Adsorption of lysozyme and fibrinogen decreased with increasing number of lactose units in the SAM, in agreement with the generally observed phenomenon that thicker hydrated layers provide higher barriers to protein adsorption. Settlement of spores of U. linza followed an opposite trend, being greater on the bulkier, more hydrated SAMs. These SAMs are more ordered for the larger saccharide units, and it is therefore hypothesized that the degree of order, and differences in crystallinity or stiffness between the surfaces, is an important parameter regulating spore settlement on these surfaces.

Hydration and chain entanglement determines the optimum thickness of poly(HEMA-co-PEG10MA) brushes for effective resistance to settlement and adhesion of marine fouling organisms.

Understanding how surface physicochemical properties influence the settlement and adhesion of marine fouling organisms is important for the development of effective and environmentally benign marine antifouling coatings. We demonstrate that the thickness of random poly(HEMA-co-PEG10MA) copolymer brushes affect antifouling behavior. Films of thicknesses ranging from 50 to 1000 Å were prepared via surface-initiated atom-transfer radical polymerization and characterized using infrared spectroscopy, ellipsometry, atomic force microscopy and contact angle measurements. The fouling resistance of these films was investigated by protein adsorption, attachment of the marine bacterium Cobetia marina, settlement and strength of attachment tests of zoospores of the marine alga Ulva linza and static immersion field tests. These assays show that the polymer film thickness influenced the antifouling performance, in that there is an optimum thickness range, 200-400 Å (dry thickness), where fouling of all types, as well as algal spore adhesion, was lower. Field test results also showed lower fouling within the same thickness range after 2 weeks of immersion. Studies by quartz crystal microbalance with dissipation and underwater captive bubble contact angle measurements show a strong correlation between lower fouling and higher hydration, viscosity and surface energy of the poly(HEMA-co-PEG10MA) brushes at thicknesses around 200-400 Å. We hypothesize that the reduced antifouling performance is caused by a lower hydration capacity of the polymer for thinner films, and that entanglement and crowding in the film reduces the conformational freedom, hydration capacity and fouling resistance for thicker films.

Tunable bioadhesive copolymer hydrogels of thermoresponsive poly(N-isopropyl acrylamide) containing zwitterionic polysulfobetaine.

This work describes a novel tunable bioadhesive hydrogel of thermoresponsive N-isopropylacrylamide (NIPAAm) containing zwitterionic sulfobetaine methacrylate (SBMA). This novel hydrogel highly regulates general bioadhesive foulants through the adsorption of plasma proteins, the adhesion of human platelets and cells, and the attachment of bacteria. In this investigation, nonionic hydrogels of polyNIPAAm, zwitterionic hydrogels of polySBMA, and three copolymeric hydrogels of NIPAAm and SBMA (poly(NIPAAm-co-SBMA)) were prepared. The copolymeric hydrogels exhibited controllable temperature-dependent swelling behaviors and showed stimuli-responsive phase characteristics in the presence of salts. The interactions of these hydrogels with biomolecules and microorganisms were demonstrated by protein adsorption, cell adhesion, and bacterial attachment, which allowed us to evaluate their bioadhesive properties. An enzyme-linked immunosorbent assay (ELISA) with monoclonal antibodies was used to measure different plasma protein adsorptions on the prepared hydrogel surfaces. At a physiological temperature, the high content of the nonionic polyNIPAAm in poly(NIPAAm-co-SBMA) hydrogel exhibits a high protein adsorption due to the interfacial exposure of polyNIPAAm-rich hydrophobic domains. A relatively high content of polySBMA in poly(NIPAAm-co-SBMA) hydrogel exhibits reduced amounts of protein adsorption due to the interfacial hydration of polySBMA-rich hydrophilic segments. The attachment of platelets and the spreading of cells were only observed on polyNIPAAm-rich hydrogel surfaces. Interestingly, the incorporation of zwitterionic SBMA units into the polyNIPAAm gels was found to accelerate the hydration of the cell-cultured surfaces and resulted in more rapid cell detachment. Such copolymer gel surface was shown to be potentially useful for triggered cell detachment. In addition, the interactions of hydrogels with bacteria were also evaluated. The polySBMA-rich hydrogels exhibited evident antimicrobial properties when they were incubated with Gram-positive bacteria ( S. epidermidis ) and Gram-negative bacteria ( E. coli ). This work shows that the bioadhesive properties of poly(NIPAAm-co-SBMA) hydrogels can be effectively controlled via regulated nonionic and zwitterionic molar mass ratios. The tunable-bioadhesive behavior of temperature-sensitive poly(NIPAAm-co-SBMA) makes this biocompatible hydrogel appropriate for biomedical applications.

Dual-thermoresponsive phase behavior of blood compatible zwitterionic copolymers containing nonionic poly(N-isopropyl acrylamide).

Thermoresponsive statistical copolymers of zwitterionic sulfobetaine methacrylate (SBMA) and nonionic N-isopropylacrylamide (NIPAAm) were prepared with an average molecular weight of about 6.0 kDa via homogeneous free radical copolymerization. The aqueous solution properties of poly(SBMA-co-NIPAAm) were measured using a UV--visible spectrophotometer. The copolymers exhibited controllable lower and upper critical solution temperatures in aqueous solution and showed stimuli-responsive phase transition in the presence of salts. Regulated zwitterionic and nonionic molar mass ratios led to poly(SBMA-co-NIPAAm) copolymers having double-critical solution temperatures, where the water-insoluble polymer microdomains are generated by the zwitterionic copolymer region of polySBMA or nonionic copolymer region of polyNIPAAm depending on temperature. A high content of the nonionic polyNIPAAm in poly(SBMA-co-NIPAAm) exhibits nonionic aggregation at high temperatures due to the desolvation of polyNIPAAm, whereas relatively low content of polyNIPAAm in poly(SBMA-co-NIPAAm) exhibits zwitterionic aggregation at low temperatures due to the desolvation of polySBMA. Plasma protein adsorption on the surface coated with poly(SBMA-co-NIPAAm) was measured with a surface plasmon resonance (SPR) sensor. The copolymers containing polySBMA above 29 mol % showed extremely low protein adsorption and high anticoagulant activity in human blood plasma. The tunable and switchable thermoresponsive phase behavior of poly(SBMA-co-NIPAAm), as well as its high plasma protein adsorption resistance and anticoagulant activity, suggests a potential for blood-contacting applications.